Patent application title: STEEL PIPE FOR VEHlCLE PIPING

Abstract:

A steel pipe has a multi-layer coating including: a plating film formed on
the surface of the steel pipe; a chemical conversion coating covering the
plating film; a primer coating covering the chemical conversion coating
and formed from a curable epoxy resin composition composed mainly of an
epoxy compound and having an amide or imide bond introduced; and a
polyamide resin coating covering the primer coating. The multi-layer
coating can significantly enhance the adhesion force of the polyamide
coating compared to the conventional pipe.

Claims:

1. A steel pipe for automotive piping, comprising a steel pipe coated with
a multi-layer coating including a plating film, wherein the multi-layer
coating comprises: a plating film formed on the surface of the steel
pipe; a chemical conversion coating covering the plating film; a primer
coating covering the chemical conversion coating and formed from a
curable epoxy resin composition composed mainly of an epoxy compound and
having an amide or imide bond introduced; and a polyamide resin coating
covering the primer coating.

2. The steel pipe for automotive piping according to claim 1, wherein the
primer coating is formed from a curable epoxy resin composition
comprising a mixture of a curable epoxy resin as a base material and a
resin having an amide or imide bond.

3. The steel pipe for automotive piping according to claim 1, wherein the
primer coating is formed from a curable epoxy resin composition
comprising a curable epoxy resin with a crosslinking structure of amide
or imide bond introduced.

4. The steel pipe for automotive piping according to claims 1, wherein the
thickness of the primer coating is 0.5 to 20 μm.

5. The steel pipe for automotive piping according to claim 1, wherein the
chemical conversion coating is a chromium-free chemical conversion
coating containing no chromium.

6. The steel pipe for automotive piping according to claim 1, wherein the
plating film is a zinc plating film formed by electroplating or hot-dip
plating.

7. The steel pipe for automotive piping according to claim 1, wherein the
polyamide resin coating is composed of PA11 or PA12.

8. The steel pipe for automotive piping according to claims 1, wherein the
steel pipe has an end portion which has undergone metal processing to
process the pipe end into a predetermined shape.

9. The steel pipe for automotive piping according to claim 8, wherein the
steel pipe has a spool, a circumferentially extending raised portion, at
the end portion.

10. The steel pipe for automotive piping according to claim 8, wherein the
steel pipe has a flare at the end portion.

11. The steel pipe for automotive piping according to claim 8, wherein the
end portion of the steel pipe has undergone drawing.

12. The steel pipe for automotive piping according to claim 11, wherein
the steel pipe is for use in automotive brake piping or fuel piping.

Description:

TECHNICAL FIELD

[0001]The present invention relates to an automotive steel pipe for use in
automotive piping, such as fuel piping or brake piping.

BACKGROUND ART

[0002]An automotive steel pipe is required to possess high properties with
respect to corrosion resistance and chemical resistance. To provide an
automotive steel pipe having enhanced corrosion resistance, it is common
practice to cover the surface of a steel pipe with a zinc plating film
and cover the plating film with a chromate conversion coating.

[0003]Automotive piping generally runs in the bottom of an automotive body
and extends to an engine. An automotive steel pipe, therefore, needs to
possess high chipping resistance so that a plating film will not be
damaged e.g. by a pebble bouncing off the road and hitting the pipe.

[0004]FIG. 3 is a cross-sectional diagram of a conventional automotive
steel pipe. In the conventional automotive steel pipe, the surface of a
steel pipe 1 is coated with a zinc plating film 2 having a thickness of 1
to 100 μm, a chromate conversion coating layer 3 is formed on the zinc
plating film 2, and the coating layer 3 is coated via a primer 4 with a
resin layer 5 having a thickness of 50 to 300 μm.

[0005]Although such a conventional automotive steel pipe has a sufficient
corrosion resistance due to the plating film 2, it is weak against impact
e.g. when it is hit by a pebble. In the case of an automotive steel pipe
for which chipping resistance is required to prevent damage to the
plating film, it is necessary to make the outermost resin layer 5 as
thick as possible to protect the zinc plating film 2. A fluororesin is
most commonly used for the resin layer 5. In conventional practice, a
primer, comprising an epoxy resin, is applied to the chromate conversion
coating layer 3, followed by baking, and thereafter the resin layer 5 is
formed by extrusion.

[0006]Instead of the costly fluororesin, a polyamide resin, which is
relatively inexpensive and has a high strength, has recently been used
for the outermost resin layer of an automotive steel pipe. When a
polyamide resin coating is employed, in order to enhance the adhesion of
the coating to a primer, an epoxy-based resin having a three-dimensional
crosslinking structure is used as a primer, or an adhesion-imparting
agent is mixed into a polyamide resin.

DISCLOSURE OF THE INVENTION

[0007]With the recent growing concern about environmental issues, biomass
fuels are becoming more and more widely used. The spread of a gasoline
fuel containing an alcohol has revealed an unexpected problem concerning
a steel pipe for use in automotive fuel piping.

[0008]When the above-described steel pipe, having a polyamide resin
coating as the outermost resin layer 5, is used in fuel piping, a fuel
contacts the resin layer 5 at a terminal joint portion of the fuel piping
at which the piping is fastened to its counterpart. In the case of the
conventional fuel, consisting solely of gasoline, contact of the fuel
with the resin layer 5 entails no significant problems.

[0009]On the other hand, in the case of a fuel which is a mixture of
gasoline with an alcohol, the alcohol adversely affects the polyamide
resin coating and the epoxy primer, causing a lowering of the adhesion of
the resin coating. This leads to poor fastening of the piping to the
counterpart, resulting in fuel leakage.

[0010]It has been confirmed by the present inventors that when the
conventional coated steel pipe is allowed to be in contact with an
alcohol fuel containing methanol in an amount of not less than 30% (vol.
%) at a temperature of not less than 80° C. for at least 72 hours,
the primer loses its adhesive force and the polyamide coating is brought
into a state in which the polyamide coating can peel off without applying
a force, i.e. the adhesion force of the polyamide coating is zero.

[0011]In such a zero adhesion state, there is a possibility of the
occurrence of a so-called tunnel leakage phenomenon in which a fuel
penetrates between the polyamide coating and the metal surface and an
O-ring, provided on the surface of the polyamide coating and sealing the
terminal fastening portion, does not work and the fuel leaks to the
outside.

[0012]The conventional automotive steel pipe also has the following
problem: Automotive steel pipes need various types of terminal
processing, such as flaring and bulging, for connection with a joint.
Such terminal processing involves severe plastic deformation.
Accordingly, peeling of the polyamide coating can occur upon terminal
processing depending on the type of the processing.

[0013]It is therefore an object of the present invention to solve the
above problems in the prior art and provide a steel pipe for automotive
piping which can significantly enhance the adhesion force of a polyamide
coating as compared to the conventional pipe and can maintain the
adhesion between the polyamide coating and the metal surface even when
the polyamide coating contacts gasoline mixed with a high-concentration
alcohol.

[0014]It is another object of the present invention to provide a steel
pipe for automotive piping which, by enhancing the adhesion force of a
polyamide coating to such a level that the coating will not peel off upon
various types of terminal processing, can be subjected to terminal
processing carried out under more severe conditions.

[0015]In order to achieve the objects, the present invention provides a
steel pipe for automotive piping, comprising a steel pipe coated with a
multi-layer coating including a plating film, wherein the multi-layer
coating comprises: a plating film formed on the surface of the steel
pipe; a chemical conversion coating covering the plating film; a primer
coating covering the chemical conversion coating and formed from a
curable epoxy resin composition composed mainly of an epoxy compound and
having an amide or imide bond introduced; and a polyamide resin coating
covering the primer coating.

[0016]In the present invention, a curable epoxy resin composition
comprising a mixture of a curable epoxy resin as a base material and a
resin having an amide or imide bond, or a curable epoxy resin composition
comprising a curable epoxy resin with a crosslinking structure of amide
or imide bond introduced.

[0017]In the present invention, the thickness of the primer coating is
preferably 0.5 to 20 μm. The chemical conversion coating preferably is
a chromium-free chemical conversion coating containing no chromium.

[0018]According to the present invention, the adhesion between the
polyamide coating and the primer coating can be significantly enhanced
compared to the conventional pipe. Further, the adhesion force of the
polyamide coating can be maintained even when the polyamide coating
contacts gasoline mixed with a high-concentration alcohol at any high
alcohol concentration and any high temperature.

[0019]In addition, according to the present invention, the adhesion force
of the polyamide coating can be enhanced to such a level that the
polyamide coating will not peel off even when the pipe end is subjected
to various types of metal processing, and therefore the pipe end can
undergo processing carried out under more severe conditions.

BRIEF DESCRIPTION OF THE DRAWINGS

[0020]FIG. 1 is a cross-sectional diagram of an embodiment of a steel pipe
for automotive piping according to the present invention;

[0021]FIGS. 2A through 2C are diagrams illustrating exemplary terminal
processing of the steel pipe for automotive piping; and

[0022]FIG. 3 is a cross-sectional diagram of a conventional steel pipe for
automotive piping.

BEST MODE FOR CARRYING OUT THE INVENTION

[0023]Preferred embodiments of the present invention will now be described
with reference to the drawings.

[0024]FIG. 1 is a diagram showing a cross-section of a steel pipe for
automotive piping according to an embodiment of the present invention. In
FIG. 1, reference numeral 10 denotes a steel pipe. In this embodiment the
steel pipe 10 is a steel pipe, having an outside diameter of 8 mm, for
use as a base pipe in automotive piping, such as fuel piping and brake
piping. The resent invention can also be applied to pipes or tubes having
various sizes in the range of 4 to 42 mm.

[0025]The outer peripheral surface of the steel pipe 10 is entirely coated
with a plating film 12. The plating film 12 preferably is a zinc plating
film, and may be formed either by electroplating or by hot-dip plating.

[0026]A chemical conversion coating 14 is formed on the entire surface of
the plating film 12. The chemical conversion coating 14 may be formed by
a chemical conversion treatment using a chromium-free chemical conversion
treatment solution containing no chromium compound, such as a hexavalent
chromium compound.

[0027]In the steel pipe for automotive piping of this embodiment, the
surface of the chemical conversion coating 14 is coated with a polyamide
resin coating 18 via a primer coating 16 so as to enhance the adhesion to
the resin coating 18. PA 11 or PA 12 can preferably be used as a resin
material.

[0028]A curable epoxy resin composition composed mainly of an epoxy
compound and having an amide or imide bond introduced is used as a
material for the primer coating 16. As the curable epoxy resin
composition may be used a curable epoxy resin composition comprising a
mixture of a curable epoxy resin as a base material and a resin having an
amide or imide bond, or a curable epoxy resin composition comprising a
curable epoxy resin with a crosslinking structure of amide or imide bond
introduced.

[0029]The primer coating 16 can be formed by dissolving the above resin
composition (molecular weight Mn not more than 100,000) in an organic
solvent, and applying the solution to the coating 14 in such an amount as
to make the thickness of the primer coating 16 after drying 0.5 to 20
μm, preferably 1 to 10 μm, followed by drying and baking at a
surface temperature of not less than 200° C.

[0030]The uppermost polyamide resin coating 18, having a thickness in the
range of 50 to 300 μm, can be formed by extrusion coating.

[0031]According to the steel pipe thus constructed, owing to the coating
structure consisting of the combination of the plating film 12, the
chemical conversion coating 14, the primer coating 16 formed from a
curable epoxy resin composition composed mainly of an epoxy compound and
having an amide or imide bond introduced, and the polyamide resin coating
18, the adhesion strength between the polyamide resin coating 18 and the
steel pipe can be significantly enhanced compared to the conventional
coated steel pipe in which a mere epoxy resin is used as a primer
material.

[0032]This is considered to be due to the fact that the interfacial
adhesion between polyamide and the chemical conversion coating 14 is
enhanced by the use of the curable epoxy resin composition having an
amide or imide bond introduced, and that the primer coating 16 itself has
an increased strength.

[0033]It has been confirmed in this connection that the enhancement of the
adhesion strength of the polyamide resin coating 18 cannot be achieved by
only using, instead of the curable epoxy resin composition, a resin
having an amide or imide bond as a material for the primer coating 16.

[0034]Because of the significantly enhanced adhesion strength of the
polyamide resin coating 18, the steel pipe for automotive piping of this
embodiment, when used in automotive fuel piping, can produce the
following advantageous effects:

[0035]When a coated steel pipe is to be used in fuel piping, the pipe end
is subjected to metal processing to process the pipe end into various
shapes, such as a spool 19, a circumferentially extending raised portion,
as shown in FIG. 2A, and a flare 20 as shown in FIG. 2B. According to the
steel pipe for automotive piping of this embodiment, peeling of the
polyamide resin coating 18 upon such terminal processing can be
prevented, thus eliminating the production of defective products.

[0036]Further, severe processing such as drawing, which is difficult to
use for the conventional coated steel pipe because of peeing of a resin
coating, becomes possible. Thus, as shown in FIG. 2C, a pipe, e.g. having
an outside diameter of 10 mm, can be narrowed at its end e.g. into 8 mm
by drawing.

[0037]In addition, it has been found that the adhesion between the
polyamide resin coating 18 and the steel pipe does not become zero even
when the coated pipe contacts a gasoline fuel containing an alcohol at a
high concentration, which is expected to be more widely used in the
future, at any mixing ratio and any temperature. This is a remarkable
effect which has never been known in conventional coated steel pipes of
this type. Further, this can prevent the occurrence of a so-called tunnel
leakage phenomenon in which a fuel penetrates between a resin coating and
a steel pipe and, despite an O-ring provided at a joint portion, the fuel
leaks out through the gap between the resin coating and the surface of
the steel pipe, lying under the sealing face of the O-ring. The
alcohol-resistant effect will be further described below with reference
to working examples.

[0038]Because of the enhancement of the adhesion strength of the polyamide
resin coating 18, a deep scratch that reaches the surface of the steel
pipe is less likely to be produced e.g. when a pebble hits the fuel
piping. The chipping resistance of the fuel piping is thus enhanced. This
also enhances the corrosion resistance.

[0039]When the steel pipe for automotive piping of this embodiment is used
in automotive brake piping, the problem of resin coating peeling upon
terminal processing can be solved as in the case of fuel piping. In the
case of brake piping, because of the high pressure in operation, it is
necessary to strongly fasten a joint portion e.g. by means of a flare
nut, which has led to the problem of breakage of a resin coating in the
conventional pipe. The steel pipe of this embodiment has the advantage
that the polyamide resin coating 18 is less likely to break even when a
joint portion is strongly fastened.

Examples

[0040]Examples of the present invention will now be described with
reference to Table 1.

[0041]In Examples 1 to 3, a coated tube was produced by carrying out
chromium-free chemical conversion treatment of a zinc-coated steel tube
having an outside diameter of 8 mm to form a chemical conversion coating,
applying a primer to the chemical conversion coating in such an amount
that the thickness of the primer coating after drying will be 1 to 10
μm, carrying out baking of the coated tube at 200° C., and then
forming a coating of PA11, having a thickness of 150 μm, by extrusion
on the primer coating. Different primer materials were used in the
Examples.

[0042]In Example 1, a curable epoxy resin composition composed of a
bisphenol A epoxy resin (EPICLON 7050, manufactured by DNC Corp.) and
polyimide (U-Varnish, manufactured by UBE Industries, Ltd.) contained in
an amount of 10 to 20% of the amount of the epoxy resin, was used as a
primer material.

[0043]In Example 2, a curable epoxy resin composition composed of the
bisphenol A epoxy resin (EPICLON 7050, manufactured by DNC Corp.) and
polyamide (2015, manufactured by ThreeBond Co., Ltd.) contained in an
amount of 10 to 20% of the amount of the epoxy resin, was used as a
primer material.

[0044]In Example 3, a curable epoxy resin composition composed of the
bisphenol A epoxy resin (EPICLON 7050, manufactured by DNC Corp.) and
polyamideimide (VYLOMAX HR, manufactured by TOYOBO Co., Ltd.) contained
in an amount of 10 to 20% of the amount of the epoxy resin, was used as a
primer material.

[0045]A peel adhesion force was measured for each coated tube in the
following manner:

[0046]Four types of ethanol-containing gasoline fuels, containing ethanol
at a concentration (vol. %) of 10% (referred to as E10), 30% (referred to
as E30), 85% (referred to as E85) and 100% (referred to as E100), were
prepared. Each of the tubes of Examples 1 to 3 was immersed in each fuel
for 72 hours while keeping the fuel at room temperature, 60° C.,
80° C. or 100° C. Thereafter, the polyamide resin coating
of each tube was cut with a knife in the axial direction of the tube to
create a cut about 2 mm long. A peel adhesion force was determined by
measuring the force necessary to peel the resin coating off the tube.

[0047]A peel adhesion force was measured also for tubes of Comparative
Examples. The tube of Comp. Example 1 uses the epoxy resin alone as a
primer material. The tube of Comp. Example 2 is another comparable
conventional tube.

[0048]As can be clearly seen from Table 1, the initial peel adhesion
forces of the tubes of Examples 1 to 3 are all higher than those of the
comparative conventional tubes. Further, the tubes of Examples exhibit
higher peel adhesion forces than the conventional tubes after contact
with the respective fuels, especially at room temperature.

[0049]As can also be seen from the data, the peel adhesion forces of the
tubes of Comp. Examples 1 and 2 can become zero after contact with the
fuels at the high temperatures, whereas the tubes of Examples 1 to 3
maintain a certain level of peel adhesion force. In addition, the tubes
of Examples 1 to 3 can maintain a certain level of peel adhesion force
for the varying ethanol concentrations of the fuel.